Dehydrogenation of hydrocarbons



Patented May 9, 1939 PATIENT OFFICE DEHYDROGENATION F HYDROCARBONS Aristld V. Grosse, Chicago, Ill., assignor to Universal Oil Products Company, Chicago, 111., a

corporation of Delaware No Drawing. Application September 30, 193i, Serial No. 166,581

g Claims. (Cl. zoo-cs6) v This invention relates particularly to dehydroof 0.25 atmospheres absolute and for times of genation of cyclic saturated hydrocarbons. In a more specific sense it is concerned with a process for selectively dehydrogenating cyclopentane 'to 5 produce relatively high yields of cyclopentadiene corresponding to the loss of 2-molecules of hydrogen.

The art of selectively dehydrogenating hydrocarbons while retaining their essential molecular 10 structure or carbon atom configuration has been developed principally upon an empirical basis and usually involves selected conditions of operation in respect to temperature, pressure, rates and the use of specially prepared catalytic materials. Even under the most carefully selected conditions particularly with the more, reactive catalysts there are numerous side reactions occurring corresponding to the degradation of the original molecules to form lower molecular weight compounds and recombin'ations of initially formed radicals to form secondary condensation products, some of which are of high molecular Weight and condensed cyclic structure. The present invention comprises a development in the art of specifically dehydrogenating hydrocarbons to produce relatively high yields of products corresponding to simple dehydrogenation reactions.

In one specific embodiment the present invention comprises the treatment of cyclopentane 30 to produce substantial'yields of cyclopenta'diene therefrom by passing the vapors of said cyclopentane over a catalyst comprising essentially the lower oxides of molybdenum on activated alumina while controlling temperature, pressure and tim of contact to produce optimum results.

Cyclopentane is the cycloparafi'in corresponding to 5 carbon atoms in the ring and having the general overall formula C5H1o. ordinary temperatures having a boiling point of 49 C. and a specific gravity of 0.7635 at 4 C. In general it has relatively greater stability, than either cyclohexane on the one hand or cyclobutane on the other, these last named compounds being those with 6 and 4 carbon atoms in the ring respectively. The structural formulas of cyclopentane and cyclopentadiene constituting the material treated and the principal product of the present process are given below:

CH2 CH CH: CH: CH O H on, on, on on Cyclopentane Cyclopentadiene 05H"; Cs u In the operation of the process of the invention cyclopentane is vaporized and passed over a particular type of granular catalyst at temperatures within the range of 500-600 C., pressures 60 from atmospheric to subatmospheric of the order It is a liquid at contact of approximately 0.5 to 6 secs. The vapors may be mixed with inert gases as an alternative method to operating under reduced pressure. The products are cooled and fractionated and cyclopentadiene recovered by fractionation or chemical methods. The major product of the reaction is a colorless liquid boiling at 41 C. which is intensely reactive and is violently attacked by both acids and alkalies. It reduces ammoniacal silver solution and rapidly polymerizes at ordinary temperatures to a bimolecular compound, dicyclopentadiene, which boils at 88 C. under a pressure of 35 mm. and which at ordinary pressures boils at 170 C. with substantial reconversion to the simple molecule of cyclopentadiene.

The preferred catalyst for use in the process under the operating conditions already specified consists of activated alumina supporting minor proportions by weight of the lower oxides of molybdenum.

It is essential to the preparation-of these catalysts that the aluminum oxide possess certain structural characteristics permitting the maintenance of a stable deposit of the molybdenum oxides on its surface which is essentially undisturbed under the conditions of operation and when regenerating by burning ofi carbonaceous deposits with air or other oxygen-containing gas mixtures. Aluminum oxide which is generally preferable as a base material for the manufacture of catalysts for the process may be obtained from some natural aluminum oxide minerals or ores nature, to wit, bauxite having the formula A12O3.2H2O and diaspore having the formula A12O3.H2O.- Of these two minerals only the corresponding oxide from the bauxite is suitable for the manufacture of the present type of catalysts and this material in some instances has given the best results of any of the base compounds whose use is at present contemplated. The mineral Dawsonite having the formula Naz'Al (C03)3.2A1(0H)a is another mineral which may be used as a source of aluminum oxide, the calcination of this mineral giving an alkalized aluminum oxide which is apparently more effective as a support in that the catalyst is more readily regenerated after a period of service.

Alumina in the form of powdered corundum is not suitable as a base.

It is best practice in the final steps of preparing aluminum oxide as a base catalyst to ignite it for some time at temperatures within the approximate range of from 600- 700 C. This does not correspond to complete dehydration of the oxide but gives a catalytic material of good strength and porosity so that it is able to resist for long periods of time the deteriorating efiects of the service and regeneration periods to which it is subjected.

Molybdenum has several oxides of which the black trioxide M003 is the most common. This oxide undergoes initial reduction by hydrogen at 300 C. to form the brown oxide M002. This reduction becomes rapid at 450 C. and the dioxide begins to reduce at 500 C. and is reduced rapidly at 600 C. The product of the reduction of the dioxide is molybdenum, the incompletely reduced product being a mixture of molybdenum and molybdenum dioxide. It will thus be evident that although the vapors of cyclopentane do not reduce the oxides of molybdenum to the same extent as hydrogen, for the provision of the desired catalytic properties it is better to operate within the lower ranges of the specified temperatures.

It has been found that there is substantially no advantage in utilizing catalysts for the present type of reaction which have more than 10% by weight of molybdenum oxides on alumina and that best practice requires about 4% when considering the efiiciency of the catalyst, cost of materials, and the cost of catalyst preparation. The use of these relatively small amounts of molybdenum oxides on the alumina apparently prevents the gradual crystallization of the oxides under the conditions of operation so that the composite catalyst has a relatively long life. Furthermore, the regeneration of the catalyst after a period of service is readily accomplished by heating in a current of air at temperatures of the same order as those employed in the dehydrogenation reactions. In the oxidizing step some pf the higher oxides may be formed which combine with the-alumina to form molybdates but these are quickly reduced and decomposed when the catalyst is again contacted with the hydrocarbon vapors.

The following example is given to indicate the general character of the results obtainable by the present process although not with the 'intentlon of unduly limiting its scope.

The general procedure in the manufacture of the catalyst was to dissolve ammonium molybdate in concentrated ammonia. and utilize this solution as a means of adding molybdenum oxides to a carrier. 20 parts by weight of ammonium molybdate was dissolved in about 50 parts by weight of concentrated aqueous ammenia and the solution then diluted by the ad-.

dition of approximately one equal volume of water. The solution was then added to about 250 parts by weight of activated alumina which had been produced by calcining bauxite at a temperature of about 700 C. followed-by grinding and sizing to produce particles of approximately 8-12 mesh. Using the proportions stated the alumina exactly absorbed the solution and the particles were first dried at 100 C. for about two hours and the temperature was then raised to 350 C. in a period of eight hours. After this calcining treatment the particles were placed in a reaction chamber and the molybdenum oxides reduced in a current of hydrogen at about 500 C., when they were then ready for service.

Vapors of cyclopentane are passed over the granular catalyst at a temperature of 500 C., an absolute pressure of 25 atmospheres and at a rate corresponding to a contact time of approximately 2 seconds. From! 8-10% of cyclopentadiene was obtained in a single pass and by recirculation of unconverted cyclopentane an ultimate yield of about 35% of cyclopentadiene was obtained. The cyclopentadiene was identified by means of its maleic anhydride addition product which melted at 162 C.

The nature of the present invention is obvious from the preceding descriptive specification and the experimental data in the example although neither section is intended to be unduly limiting.

I claim as my invention:

1. A process for dehydrogenating cyclopentane to produce substantial yields of cyclopentadiene which comprises vaporizing said cyclopentane and passing the vapors under dehydrogenating conditions over a granular catalyst comprising essentially a major proportion of activated alumina supporting a minor proportion of oxides of molybdenum.

2. A process for dehydrogenating cyclopentane to produce substantial yields of cyclopentadiene which comprises vaporizing said cyclopentane and passing the vapors at a temperature within the range of 500-600 C. over a granular catalyst comprising essentially a major proportion of activated alumina supporting a minor proportion of an oxide of molybdenum.

3. A process for dehydrogenating cyclopentane to produce substantial yields of cyclopentadiene which comprises vaporizing said cyclopentane and passing the vapors at a temperature within the range of 500-600 C. under pressures of from 0.25 to 1 atmosphere absolute 'over a granular catalyst comprising essentially a major proportion of activated alumina supporting a minor proportion of an oxide of molybdenum.

4. A process for dehydrogenating cyclopentane to produce substantial yields of cyclopentadiene which comprises vaporizing said cyclopentane and passing the vapors at a temperature within the range of 500-600 C. under pressures of from 0.25 to 1 atmosphere absolute for times of from 0.5 to 6 seconds over a granular catalyst comprising essentially a major proportion of activated alumina supporting a minor proportion of an oxide of molybdenum.

5. A process for dehydrogenating cyclopentane to produce substantial yields of cyclopentadiene which comprises vaporizing said cyclopentane and passing the vapors at a temperature within the range of 500-000 C. under pressures of from 0.25 to 1 atmosphere absolute for times of from 0.5 to 6 seconds over a granular catalyst com prising essentially a major proportion of activated alumina supporting a minor proportion of an oxide of molybdenum, recovering cyclopentadiene from the products and returning unconverted cyclopentane to the dehydrogenation zone for further dehydrogenation.

ARISTID V. GROSSE. 

